Vat dyestuffs of the phthaloylcarbazolo triazine series



United States Patent "ice Patented 5,5311:

dyestuffs of the present invention that they possess colors from brown to bordeaux to olive green. It is not known 2729638 why the new series of triazine vat dyestuifs possess these VAT DYESTUFFS OF THE PHTHALOYLCARBA. deep shades, especially those of a greenish shade, when ZOLO TRIAZINE SERIES 5 the known triazine vat dyes are yellows to reds and it is not intended to limit the invention to any theory of why the carbazole or anthraquinonylaminophenyl groups show so marked a color difference.

Asa Willard Joyce, Plainfield, N. L, assignor to American Cyanamid ompany, New York, N. Y., a corporation of Mame The invention is not limited to any particular process No Drawing. Application December 17, 1953, of producing the dyestuffs. It is however an advantage Serial No. 393,876 thatthey can be produced by a very simple process in good 18 Claims- (CL 260-249) yield and without operating difficulties. The process as applied to the preferred dyestufis which contain an alphabenzoylamino group in the anthraquinone nucleus are This invention relates to a new series of vat dyestufis represented by the following equation:

which are 2-phthal0ylcarbazolophenyl 4,6 alpha-amh In this equation- Y represents a halogen atom, X is an quinonylamino 1,3,5 triazines. The invention also inalpha-beflleylamme groups and Q Stands P the p cludes a new series of intermediates from which the dyeflmhraqllinonyl Tedleale alpha'anthraqumonylphenyl stuifs are made which are 2-(ortho-alpha-anthraquinonyltIiaZineS Obtained y e condensation can lhell be Iillg amino phenyl) 4,6 di (alpha-anthraquinonylamino) 1,3,5 closed to the corresponding carbazoles. It IS an advantriazines. The carbazole containing dyestuffs have the tage of the Present Invention that the first p can be f l simply effected using high boiling inert solvents such as naphthalene, nitrobenzene, dichlorobenzene, and the like in the presence of a cupriferous substance which exerts j its well-known catalytic efliect and an acid binding agent AQ such as sodium carbonate, sodium acetate or the like to unite with the hydrogen halide set free by the reaction. 1 NH 40 The ring closure is likewise efiected simply by a procedure which presents no operating problems and which may if N advantageously use an acid ring closing agent such as aluminum chloride. The ring closing step is also prefer- AAQNH \N) NHAAQ ably carried out in a solvent such as nitrobenzene.

The alpha-benzoylamino group may be unsubstituted or it may carry substituents such as alkyl or alkoxy. Typical of such substituted alpha-benzoylamino groups are ortho-toluylamino or anisoylamino.

The invention will be described in greater detail in conjunction with the following specific examples in which the parts are by weight unless otherwise specified.

Example 1 in which [AQ is an anthraquinone radical linked to the NH at an alpha position and AAQ is an alpha-anthraquinonyl radical. The intermediates have the formula NHAAQ in which AAQ stands for an alpha-anthraquinonyl radical. More specifically in a preferred embodiment the invention relates to 2-carbazolophenyl triazine dyestuffs having the formula given above in which the group AQ contains an alpha-benzoylamino group. The preferred dyestuffs not only have high fastness and excellent dyeing properties but they are almost unique among triazine vat dyes in their color. Triazine vat dyes which contain an aryl group and two anthraquinonyl groups are in general yellows to reds. There has long been a demand for triazine vat dyestuifs having a deeper shade and it is an important property of the preferred One hundred parts of naphthalene are melted at 100 C To this is added 12.7 parts of 2-(o-chlorophenyl)-4,6-di- (alpha-anthraquinonyl) 1,3,5-triazine, 6.9 parts of 1- amino-4-benzamidoanthraquinone, 5 parts of sodium carbonate, 3 parts of anhydrous sodium acetate, and 0.5 part of cuprous bromide. This mixture is stirred at 205 C. until the reaction is substantially complete. It is then cooled to 150 C. and diluted with 185 parts of chlorobenzene. The mixture is then cooled to 100 C. and the product is isolated by filtration and washing with chlorobenzene. The dye cake is steamed to remove solvent and then extracted with hydrochloric acid to remove inorganic materials. The dry product is a dark brown powder which dissolves in concentrated sulfuric acid with a green coloration, and dyes cotton strong, fast, olive green shades from a dark red vat.

Example 2 Twelve parts of anhydrous aluminum chloride and 40 parts of mononitrobenzene are fused at 50 C. Six parts of the dyestufi prepared in Example 1 is added gradually, and the melt is then heated gradually to 75 C. The mixture is then drowned in an excess of dilute sodium hydroxide. Mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 1.

Example 3 The procedure of Example 1 is repeated replacing the l-amino-4-benzamidoanthraquinone with an equivalent amount of 1-amino-4-o-toluylamidoanthraquinone. A good yield of dyestufi is obtained which dyes cotton an olive green shade.

Twelve parts of anhydrous aluminum chloride and 40 parts of mononitrobenzene are fused at 50 C. Six parts of the dyestufl prepared in Example 3 is added gradually, and the melt is then heated gradually to C. The mixture is then drowned in an excess of dilute soduim hydroxide. Mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 3.

Example 5 N N NHiN NH The procedure of Example 1 is repeated substituting for the 1-amino-4-benzamidoanthraquinone an equivalent amount of l-amino-4-p-toluylamidoanthraquinone. A good yield of dyestuff is obtained which dyes a cotton a shade substantially similar to that of Example 3.

Example 6 Twelve parts of anhydrous aluminum chloride and 40 parts of mononitrobenzene are fused at 50C. Six parts of the dyestufi prepared in Example 5 is added gradually, and the melt is then heated gradually to 75 C. The mixture is then drowned in an excess of dilute sodium hydroxide. Mononitrobenzene is removed by steaming, and the product is isolated by filtration and Washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 5.

Example 7 The procedure for Example 1 is repeated replacing the l-amino-4-benzamidoanthraquinone with an equivalent amount of l-amino-4-0-methoxybenzamidoanthraquinone. A good yield of dyestufl is obtained which dyes cotton an olive green shade. A similar result is obtained with 1-amino-4-p-methoxybenzamidoanthraquinone.

' 6 Example:8

Twelve parts of anhydrous aluminum chloride and 4.0 parts of mononitrobenzene are fused at 50 C. Six parts of the dyestufi prepared in Example 7 is added gradually, and the melt is then heated gradually to 75 C. The mixture is then drowned in an excess of dilute sodium hydroxide. Mononitrobenzene is removed by steaming, and the product is-isolated by filtration and washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 7.

Example 9 O -NH 0011.

N NH k J-NH o N o The procedure of Example 1 is repeated replacing the l-amino-4-benzamidoanthraquinone with an equivalent amount of 1-amino-4-m-methoxybenzamidoanthraquinone. A good yield of the dyestuff is obtained which dyes cotton olive shades.

7 Example 10 (])GHI O NHC o-G O l 0 N N o m gi,

Twelve parts of anhydrous aluminum chloride and 40 parts of mononitrobenzene are fused at 50 C. Six parts of the dyestulf prepared in Example 9 is added gradually, and the melt is then heated gradually to 75 C. The mixture is then drowned in an excess of dilute sodium hydroxide. Mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 9.

The procedure of Example 1 is followed replacing the 1-amino-4-benzamidoanthraquinone with an equivalent amount of alpha-aminoanthraquinone. The dyestulf is obtained in good yield which dyes cotton olive shades.

Example 12 N Ml lNH Twelve parts of anhydrous aluminum chloride and parts of mononitrobenzene are fused at C. Six parts of the dyestutf prepared in Example 11 is added gradually, and the melt is then heated gradually to C. The mixture is then drowned in an excess of dilute sodium hydroxide. Mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. It is an olive green solid dyeing a somewhat yellower shade than the product of Example 11.

Example 13 O NH Ten and five-tenths parts of 2-(o-chlorophenyl)-4,6-di(4- benzamido 1 anthraquinonylamino)-l,3,5-triazine, 4.1 parts of 1-amino-4-benzamidoanthraquinone, 3 parts of sodium carbonate, 1.5 parts of anhydrous sodium acetate, and 0.3 part of cuprous bromide are introduced into 75 parts of molten naphthalene at about 100 C. The mixture is then stirred at 205-2l0 C. until the reaction is substantially complete. It is cooled to 150 C. and diluted with 100 parts of chlorobenzene. It is then cooled 10 Ten parts of anhydrous aluminum chloride and parts of mononitrobenzene are fused at C. Three and five-tenths parts of the product of Example 13 is added gradually and the mixture is stirred at 60-65 C. until the reaction is substantially complete. The mixture is V thendrowned in an excess of dilute sodium hydroxide.

The mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. An excellent vyield is obtained of a product which dyes cellulose further to about C., and the product is isolated by 10 fabrics fast brown shades from a red vat.

filtration and washing with chlorobenzene and acetone. The inorganic impurities are then removed by extraction with diluted hydrochloric acid. The dyestufi, obtained in 5 excellent yield, dissolves in concentrated sulfuric acid with a red coloration, and dyes cotton Bordeaux red shades of good fastness and color value from a red brown vat.

Example 14 Example 15 0... NLN

The procedure of Example 13 is followed but the starting material is replaced with the same weight of 2-(ochlorophenyl) 4,6 di(5f benzamido 1' anthraquinonylamino)-l',3,5-triazine. A dyestuii is obtained which dyes cotton a yellower shade of Bordeaux red than in the case of Example 13.

Example I 6 NH-G ml NH Ten parts of anhydrous aluminum chloride and 40 parts 1,3,5-triazine. A dyestulf is obtained which dyes cotton of mononitrobenzene are fused at 60 C. Three and Bordeaux red shades of about the same color as Example five-tenths parts of the product of Example 15 is added 15, that is to say yellower than Example 13.

gradually and the mixture is stirred at 60-65 C. until the reaction is substantially complete. The mixture is then drowned in an excess of dilute sodium hydroxide.

The mononitrobenzene is removed by steaming, and the product is isolated by filtration and washing. An excellent yield is obtained of a production which dyes cellulose Example 18 fabrics fast brown shades from a red vat.

\NH Example 17 0 O N N O H L J H N N N o NH-C 00 o 0 N N NH-CO CO-NH -Nni J-NH o N o NH-CO CO-NH Ten parts of anhydrous aluminum chloride and 40 parts of mononitrobenzene are fused at 60 C. Three and fivetenths parts of the product of Example 17 is added gradually and the mixture is stirred at 60-6S C. until the reaction is substantially complete. The mixture is then drowned in an excess of dilute sodium hydroxide. The

mononitrobenzene is removed by steaming, and the prod- The procedure of Example 15 is repeated replacing the not is isolated by filtration and washing. An excellent starting material of the same weight of 2-(o-chlorophenyield is obtained of a product which dyes cellulose fabrics yl) 4,6 di(8 benzamido- 1' anthraquinonylaminoj- 5 fast brown shades from a red vat.

Example 19 Y r -NE-k J-NH N o Ten and five-tenths parts of 2-(o-chlorophenyl)-4,6-diis a member of the group consisting of (4' benzamido l anthraquinonylamino) 1,3,5 triazine, 4.1 parts of 1-amino-5-benzamidoanthraquinone,

3 parts of sodium carbonate, 1.5 parts of anhydrous sodium acetate, and 0.3 part of cuprous bromide are added to 75 parts of molten naphthalene at about 100 C. The mixture is then stirred at 205 210 C. until the reaction is substantially complete. The mass is cooled to about 150 C. and diluted with 150 parts of chloro- AQ benzene. The mixture is filtered and the product is Washed with chlorobenzene and acetone. Inorganic im- \NH purities are removed by hot extraction with dilute hydrochloric acid. The dyestuff, obtained in excellent yield, v dissolves in concentrated sulfuric acid with a violet-red where AAQ has the same meaning as above and [AQ is color and dyes cellulose fibers strong copper-brown shades an anthraquinone radical linked to the NH in an alpha of excellent fastness from a violet-brown vat. position.

Example 20 The procedure of Example 18 is followed except that 2. Compounds having the formula instead of using the product of Example 15 an equivalent amount of the product of Example 19 is used. An excellent yield of dyestufi is obtained which dyes cellulose fabrics fast brown shades which are a somewhat yellower 5 shade of brown than in the case of dyestufi of Example 16.

I claim:

1. Compounds of the formula N N N N AAQNHLNJNHAAQ in which AAQ is an alpha-anthaquinonyl radical and X in which AAQ is an alpha-anthraquinonyl radical.

in which AAQ stands for an alpha-anthraquinonyl radical and [AQ stands for an anthraquinone radical linked to the NH in an alpha position.

4. Compounds according to claim 2 in which the alpha-anthraquinonylamino group attached to the phenyl group is substituted by an alpha-benzoylamino group.

5. Products according to claim 3 in which the radical [AQ contains an alpha-benzoylamino substituent.

6. Compounds according to claim 2 in which the alphaanthraquinonyl group attached to phenyl contains a S-benzoylamino group.

7. Compounds according to claim 2 in which the alphaanthraquinonylamino group attached to phenyl contains a 4-benzoylamino group.

8. Compounds according to claim 3 in which the anthraquinone radical [AQ contains a 4-benzoylamino substituent.

9. Compounds according to claim 3 in which the anthraquinone group [AQ contains a 5-benzoylamino substituent.

10. Compounds according to claim 2 in which the alpha-anthraquinonylamino groups attached to the triazine ring contain each a benzoylamino group as a substituent.

11. Products according to claim in which the henzoylamino group is in the 4 position.

12. Compounds according to claim 3 in which each of the alpha-anthraquinonylamino groups attached to the triazine ring carries an alpha-benzoylamino group as a substituent.

13. Products according to claim 12 in which the henzoylamino substituent is on the 4 position.

14. The new compound of the structure 15. The new compound having the structure 16. The new compound having the structure NH- 0 O N N 0 NH-L NH 0 I N ii NE 17. The new compound having the structure NHOO I NH O I N N NHLN H p 18. The new compound of the structure NE NH GreatBritain June 24, 1936 France 1936 

1. COMPOUNDS OF THE FORMULA 